Organodisilane precursors for ALD/CVD silicon-containing film applications

ABSTRACT

Disclosed are Si-containing film forming composition comprising organodisilane precursors. The organodisilane precursors have the formula (E-(CR) n -E)SiH 2 —SiH x (E-(CR) n -E) 3-x , wherein x is 2 or 3; each n is independently 1 or 3; each (E-(CR) n -E) group is a monoanionic bidentate ligand bonding to the Si through each E; each E is independently chosen from NR, O or S; and each R is independently selected from the group consisting of H, a C1 to C6 alkyl group, and a C3-C20 aryl or heterocycle group. Also disclosed are methods of synthesizing the Si-containing film forming compositions and methods of using the same to deposit silicon-containing films using vapor deposition processes for manufacturing semiconductors, photovoltaics, LCD-TFT, flat panel-type devices, refractory materials, or aeronautics.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a 371 of International PCT Application No.PCT/US2015/053818 filed Oct. 2, 2015, which claims the benefit of U.S.Provisional Application Ser. No. 62/059,060 filed Oct. 2, 2014, theentire contents of both herein incorporated by reference in its entiretyfor all purposes.

TECHNICAL FIELD

Disclosed are Si-containing film forming compositions comprisingorganodisilane precursors. The organodisilane precursors have theformula (E-(CR)_(n)-E)SiH₂—SiH_(x)(E-(CR)_(n)-E)₃, wherein x is 2 or 3;each n is independently 1 or 3; each (E-(CR)_(n)-E) group is amonoanionic bidentate ligand bonding to the Si through each E; each E isindependently chosen from NR, O or S; and each R is independentlyselected from the group consisting of H, a C1 to C6 alkyl group, and aC3-C20 aryl or heterocycle group. Also disclosed are methods ofsynthesizing the Si-containing film forming compositions and methods ofusing the same to deposit silicon-containing films using vapordeposition processes for manufacturing semiconductors, photovoltaics,LCD-TFT, flat panel-type devices, refractory materials, or aeronautics.

BACKGROUND

Si-containing thin films are used widely in the semiconductor,photovoltaic, LCD-TFT, flat panel-type device, refractory material, oraeronautic industries. Si-containing thin films may be used, forexample, as dielectric materials having electrical properties which maybe insulating (SiO₂, SiN, SiCN, SiCOH, MSiO_(x), wherein M is Hf, Zr,Ti, Nb, Ta, or Ge, and x is greater than zero), Si-containing thin filmsmay be used as conducting films, such as metal silicides or metalsilicon nitrides. Due to the strict requirements imposed by downscalingof electrical device architectures towards the nanoscale (especiallybelow 28 nm node), increasingly fine-tuned molecular precursors arerequired which meet the requirements of volatility (for ALD process),lower process temperatures, reactivity with various oxidants and lowfilm contamination, in addition to high deposition rates, conformalityand consistency of films produced.

Hunks et al. disclose a wide range of Si-containing precursors inUS2010/0164057, including silicon compounds having the formulaR_(4-x)SiL_(x), wherein x is an integer having a value from 1 to 3; Rmay be selected from H, branched and unbranched C1-C6 alkyl, C3-C8cycloalkyl, and C6-C13 aryl groups; and L may be selected fromisocyanato, methylethylketoxime, trifluoroacetate, triflate, acyloxy,μ-diketiminate, μ-diiminate, amidinate, guanidinate, alkylamino,hydride, alkoxide, or formate ligands. Pinnavaia et al. claim a methodfor the preparation of a porous synthetic, semi-crystalline hybridorganic-inorganic silicon oxide composition from silicon acetylacetonateand silicon 1,3-diketonate precursors (U.S. Pat. No. 6,465,387).

In Proceedings of SPIE 2438, Advances in Resist Technology andProcessing XII, 762 (Jun. 9, 1995), Wheeler et al. discloseaminodisilanes used as silylating reagents for near-surface imaging withdeep-UV (248 nm) and EUV (13.5 nm) lithography.

Disilane containing precursors bearing both alkyl and amino groups havebeen disclosed for deposition of SiCN thin films by Tsukada andDussarrat in JP 2006096675.

Xiao et al. disclose another family of Si-containing precursors inUS2013/0323435 which have the formula (R¹R²N)_(n)—SiH_(3-n)SiH₃ whereinR¹ is selected from linear or branched C3 to C10 alkyl group, linear orbranched C3 to C10 alkenyl group, linear or branched C3 to C10 alkynylgroup, C1 to C6 dialkylamino group, electron withdrawing group, and C6to C10 aryl group; R² is selected from hydrogen, linear or branched C1to C10 alkyl group, linear or branched C3 to C6 alkenyl group, linear orbranched C3 to C6 alkynyl group, C1 to C6 dialkylamino group, C6 to C10aryl group, linear or branched C1 to C6 fluorinated alkyl group,electron withdrawing group, and C4 to C10 aryl group; optionally whereinR¹ and R² are linked together to form ring selected from substituted orunsubstituted aromatic ring or substituted or unsubstituted aliphaticring; and n=1 or 2.

Additionally, Xiao et al also disclose another family of Si-containingprecursors in US2013/0319290 which have the formula(R¹R²N)—SiH₂SiH₂—(NR³R⁴) and methods for forming silicon-containingfilms and wherein R¹ and R³ are independently selected from linear orbranched C3 to C10 alkyl group, a linear or branched C3 to C10 alkenylgroup, a linear or branched C3 to C10 alkynyl group, a C1 to C6dialkylamino group, an electron withdrawing and a C6 to C10 aryl group;R2 and R4 are independently selected from hydrogen, a linear or branchedC3 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, alinear or branched C3 to C10 alkynyl group, a C1 to C6 dialkylaminogroup, an electron withdrawing, and a C6 to C10 aryl group; and whereinany one, all, or none of R¹ and R², R³ and R⁴, R¹ and R³, or R² and R⁴are linked to form a ring.

Recently Dussarrat et al. disclosed silicon amidinate precursors inWO2014/015232, which have the form H₃Si(amd), and silicon β-diketiminateprecursors in WO2014/015237, each of which demonstrate the utility ofthe chelating ligand framework to support the —SiH₃ functionality. Thesame authors also disclosed related oxygen containing precursors basedupon chelating O—O and N—O delocalized ligand frameworks [seeWO2014/015241 and WO2014/015248, respectively].

Sanchez et al. disclose compounds and methods of preparation of Si—X andGe—X compounds (X═N, P, As, Sb) via dehydrogenative coupling between thecorresponding unsubstituted silanes and amines (including NH₃) andphosphines catalyzed by metallic catalysts (US2015/0094470).

Despite the wide range of choices available for the deposition of Sicontaining films, additional precursors are continuously sought toprovide device engineers the ability to tune manufacturing processrequirements and achieve films with desirable electrical and physicalproperties.

Notation and Nomenclature

Certain abbreviations, symbols, and terms are used throughout thefollowing description and claims, and include:

As used herein, the indefinite article “a” or “an” means one or more.

As used herein, the terms “approximately” or “about” mean±10% of thevalue stated.

As used herein, the term “independently” when used in the context ofdescribing R groups should be understood to denote that the subject Rgroup is not only independently selected relative to other R groupsbearing the same or different subscripts or superscripts, but is alsoindependently selected relative to any additional species of that same Rgroup. For example in the formula MR¹ _(x)(NR²R³)_((4-x)), where x is 2or 3, the two or three R¹ groups may, but need not be identical to eachother or to R² or to R³. Further, it should be understood that unlessspecifically stated otherwise, values of R groups are independent ofeach other when used in different formulas.

As used herein, the term “alkyl group” refers to saturated functionalgroups containing exclusively carbon and hydrogen atoms. Further, theterm “alkyl group” refers to linear, branched, or cyclic alkyl groups.Examples of linear alkyl groups include without limitation, methylgroups, ethyl groups, propyl groups, butyl groups, etc. Examples ofbranched alkyls groups include without limitation, t-butyl. Examples ofcyclic alkyl groups include without limitation, cyclopropyl groups,cyclopentyl groups, cyclohexyl groups, etc.

As used herein, the term “aryl” refers to aromatic ring compounds whereone hydrogen atom has been removed from the ring. As used herein, theterm “heterocycle” refers to a cyclic compound that has atoms of atleast two different elements as members of its ring.

As used herein, the abbreviation “Me” refers to a methyl group; theabbreviation “Et” refers to an ethyl group; the abbreviation “Pr” refersto any propyl group (i.e., n-propyl or isopropyl); the abbreviation“iPr” refers to an isopropyl group; the abbreviation “Bu” refers to anybutyl group (n-butyl, iso-butyl, t-butyl, sec-butyl); the abbreviation“tBu” refers to a tert-butyl group; the abbreviation “sBu” refers to asec-butyl group; the abbreviation “iBu” refers to an iso-butyl group;the abbreviation “Ph” refers to a phenyl group; the abbreviation “Am”refers to any amyl group (iso-amyl, sec-amyl, tert-amyl); theabbreviation “Cy” refers to a cyclic alkyl group (cyclobutyl,cyclopentyl, cyclohexyl, etc.); the abbreviation “R-fmd” refers to anR—N—C(H)—N—R formamidinate ligand, with R being an alkyl group (e.g.,iPr-fmd is iPr—N—C(H)—N-iPr); and the abbreviation “R-amd” refers to anR—N—C(Me)-N—R amidinate ligand, with R being an alkyl group (e.g.,iPr-amd is iPr—N—C(Me)-N-iPr).

As used herein, the acronym “SRO” stands for a Strontium Ruthenium Oxidefilm; the acronym “HCDS” stands for hexachlorodisilane; and the acronym“PCDS” stands for pentachlorodisilane.

The standard abbreviations of the elements from the periodic table ofelements are used herein. It should be understood that elements may bereferred to by these abbreviations (e.g., Si refers to silicon, N refersto nitrogen, O refers to oxygen, C refers to carbon, etc.).

SUMMARY

Si-containing film forming compositions comprising organodisilaneprecursors are disclosed. The organodisilane precursors have thefollowing formula are disclosed:(E-(CR)_(n)-E)SiH₂—SiH_(x)(E-(CR)_(n)-E)_(3-x)wherein x is 2 or 3; each n is independently 1 or 3; each (E-(CR)_(n)-E)group is a monoanionic bidentate ligand bonding to the Si through eachE; each E is independently chosen from NR, O or S; and each R isindependently selected from the group consisting of H, a C1 to C6 alkylgroup, and a C3-C20 aryl or heterocycle group. The Si-containing filmforming compositions may have one or more of the following aspects:

-   -   R being a C1 to C6 alkyl group;    -   Each R independently being H, Me, Et, Pr, or Bu;    -   x being 3;    -   n being 1;    -   having the formula:

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-   -   the Si-containing film forming composition comprising between        approximately 0.1 molar % and approximately 50 molar % of the        organodisilane precursor;    -   the Si-containing film forming composition comprising between        approximately 93% w/w to approximately 100% w/w of the        organodisilane precursor;    -   the Si-containing film forming composition comprising between        approximately 99% w/w to approximately 100% w/w of the        organodisilane precursor;    -   the Si-containing film forming composition comprising between        approximately 0% w/w and 5% w/w of hexane, substituted hexane,        pentane, substituted pentane, dimethyl ether, or anisole;    -   the Si-containing film forming composition comprising between        approximately 0 ppmw and 200 ppmw of Cl;    -   further comprising a solvent;    -   the solvent being selected from the group consisting of C1-C16        hydrocarbons, THF, DMO, ether, pyridine, and combinations        thereof;    -   the solvent being a C1-C16 hydrocarbon;    -   the solvent being tetrahydrofuran (THF);    -   the solvent being dimethyl oxalate (DMO);    -   the solvent being ether;    -   the solvent being pyridine;    -   the solvent being ethanol; or    -   the solvent being isopropanol.

Also disclosed is a Si-containing film forming composition deliverydevice comprising a canister having an inlet conduit and an outletconduit and containing any of the Si-containing film formingcompositions disclosed above. The disclosed device may include one ormore of the following aspects:

-   -   the Si-containing film forming composition having a total        concentration of metal contaminants of less than 10 ppmw;    -   an end of the inlet conduit end located above a surface of the        Si-containing film forming composition and an end of the outlet        conduit located below the surface of the Si-containing film        forming composition;    -   an end of the inlet conduit end located below a surface of the        Si-containing film forming composition and an end of the outlet        conduit located above the surface of the Si-containing film        forming composition;    -   further comprising a diaphragm valve on the inlet and the        outlet;    -   the Si-containing film forming composition being:

Also disclosed are methods of depositing a Si-containing layer on asubstrate. The vapor of any of the Si-containing film formingcompositions disclosed above is introduced into a reactor having asubstrate disposed therein. At least part of the organodisilaneprecursor is deposited onto the substrate to form a Si-containing layerusing a vapor deposition method. The disclosed methods may have one ormore of the following aspects:

-   -   introducing into the reactor a vapor comprising a second        precursor;    -   the second precursor comprising an element selected from the        group consisting of group 2, group 13, group 14, transition        metal, lanthanides, and combinations thereof;    -   the element of the second precursor being selected from Mg, Ca,        Sr, Ba, Zr, Hf, Ti, Nb, Ta, Al, Si, Ge, Y, or lanthanides;    -   introducing a co-reactant into the reactor;    -   the co-reactant being selected from the group consisting of O₂,        O₃, H₂O, H₂O₂, NO, NO₂, a carboxylic acid, radicals thereof, and        combinations thereof;    -   the co-reactant being plasma treated oxygen;    -   the co-reactant being ozone;    -   the Si-containing layer being a silicon oxide layer;    -   the co-reactant being selected from the group consisting of H₂,        NH₃, (SiH₃)₃N, hydridosilanes (such as SiH₄, Si₂H₆, Si₃H₈,        Si₄H₁₀, Si₅H₁₀, Si₆H₁₂), chlorosilanes and chloropolysilanes        (such as SiHCl₃, SiH₂Cl₂, SiH₃Cl, Si₂Cl₆, Si₂HCl₅, Si₃Cl₈),        alkysilanes (such as Me₂SiH₂, Et₂SiH₂, MeSiH₃, EtSiH₃),        hydrazines (such as N₂H₄, MeHNNH₂, MeHNNHMe), organic amines        (such as NMeH₂, NetH₂, Nme₂H, NEt₂H, Nme₃, NEt₃, (SiMe₃)₂NH),        pyrazoline, pyridine, B-containing molecules (such as B₂H₆,        9-borabicylo[3,3,1]none, trimethylboron, triethylboron,        borazine), alkyl metals (such as trimethylaluminum,        triethylaluminum, dimethylzinc, diethylzinc), radical species        thereof, and mixtures thereof;    -   the co-reactant being selected from the group consisting of H₂,        NH₃, SiH₄, Si₂H₆, Si₃H₈, SiH₂Me₂, SiH₂Et₂, N(SiH₃)₃, hydrogen        radicals thereof, and mixtures thereof;    -   the co-reactant being HCDS or PCDS;    -   the vapor deposition method being a chemical vapor deposition        process;    -   the vapor deposition method being an atomic layer deposition        (ALD) process;    -   the vapor deposition method being a spatial ALD process;    -   the silicon-containing layer being Si;    -   the silicon-containing layer being SiO₂;    -   the silicon-containing layer being SiN;    -   the silicon-containing layer being SiON;    -   the silicon-containing layer being SiCN; and    -   the silicon-containing layer being SiCOH.

Also disclosed are methods of forming Si-containing films on substrates.A solution comprising any of the Si-containing film forming compositionsdisclosed above is contacted with the substrate and the Si-containingfilm formed via a spin coating, spray coating, dip coating, or slitcoating technique. The disclosed methods may include the followingaspects:

-   -   the Si-containing film forming composition comprising ethanol;    -   the Si-containing film forming composition comprising        isopropanol;    -   forming the Si-containing film via a spin coating technique;    -   forming the Si-containing film via a spray coating technique;    -   forming the Si-containing film via a dip coating technique;    -   forming the Si-containing film via a slit coating technique;    -   annealing the Si-containing film; or    -   laser treating the Si-containing film.

BRIEF DESCRIPTION OF THE DRAWINGS

For a further understanding of the nature and objects of the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying drawings, inwhich like elements are given the same or analogous reference numbersand wherein:

FIG. 1 is a side view of one embodiment of the Si-containing filmforming composition chemistry delivery device disclosed herein; and

FIG. 2 is a side view of a second embodiment of the Si-containing filmforming delivery device disclosed herein.

DESCRIPTION OF PREFERRED EMBODIMENTS

Si-containing film forming compositions comprising organodisilaneprecursors are disclosed. The organodisilane precursors have thefollowing formula:(E-(CR)_(n)-E)SiH₂—SiH_(x)(E-(CR)_(n)-E)_(3-x)wherein x is 2 or 3, each n is independently 1 or 3, each (E-(CR)_(n)-E)group is a monoanionic bidentate ligand bonding to the Si through eachE, each E is independently chosen from O, S, or NR, and each R isindependently H, a C1 to C6 alkyl group, or a C3-C20 aryl or heterocyclegroup.

The disclosed organodisilane precursors are derived from differentclasses of ligand systems, such as diketiminate, diketonate,ketoiminate, amidinate, thiodiketonate, dithiodiketonate, and/orthioketiminate ligands. The specific design of these precursors may helpimprove volatility, reduce the melting point (liquids or very lowmelting solids), increase reactivity with water, and increase thermalstability for wider process window applications.

As illustrated below, the E atoms are bonded to the silicon atom,resulting in a pentacoordinate Si(IV) center. The carbon atom in thebackbone of the bidentate monoanionic ligand is sp² hybridized,resulting in a delocalized charge across the monoanionic ligand. Thecarbon atoms may independently be substituted by H, C1-C6 alkyl groups,aryl groups, or heterocycle groups.

The disclosed organodisilane precursors may be more reactive than otheramino-substituted organodisilane precursors due to hypercoordination atone or both silicon atoms. In other words, although the silicon atom is+IV, the two Si—H bonds, one Si—Si bond, and the monoanionic chelatingligand results in a total of 5 bonds to the silicon atom.

The organodisilane precursor contains four or five hydrogen atomsdirectly bonded to the Si atom. These Si—H bonds may help increase thevolatility of the precursor. The disclosed organodisilane precursorscontain no Si-halogen bonds which is important because halogens maydamage other layers in the substrate (e.g., low k layers, copperinterconnect layers, etc.). Additionally, in ALD processes, the four orfive Si—H bonds of the disclosed precursors may help to provide a largergrowth rate per cycle when compared to the analogous Si-halogencontaining precursors because the H atoms occupy less surface area,resulting in more molecules on the substrate surface. Inclusion of theSiH bonds (i.e., hydride functionality) may produce less steric bulk,which may allow the precursors higher reactivity to the substrate.

Each E may be NR. Due to their increased nitrogen content when comparedto the when any of L¹ through L⁴ is an oxygen or sulfur atom, thesemolecules may be used to produce silicon-containing films that alsocontain nitrogen, such as SiN, SiCN, SiON, MSiN, or MSiON, wherein M isan element such as Hf, Zr, Ti, Nb, Ta, or Ge, or to tune the amount ofnitrogen in those films.

One of ordinary skill in the art will recognize that embodiments inwhich n=1 may produce precursors having higher volatility and lowermelting points, being more suitable for vapor deposition. Embodiments inwhich n=3 may also be suitable for vapor deposition when the resultingsilicon-containing film also contains carbon. Embodiments in which n=3may also be suitable for casting deposition methods, such as spin-on ordip coating.

Exemplary organodisilane precursors wherein x=3, n=1, and each E=NRcontain both amidinate and hydride functionalities and have thefollowing formula:

wherein R¹, R² and R³ is independently H, a C1 to C6 alkyl group, or aC3-C20 aryl or heterocycle group. R¹ and R² and/or R¹ and R³ may bejoined to form cyclic chains.

Exemplary mono(formamidinato)disilanes include:

Exemplary mono(amidinato)disilanes include:

Exemplary organodisilane precursors wherein x=2, each n=1, and each E=NRcontain both amidinate and hydride functionalities and have thefollowing formula:

wherein R¹, R², R³, R⁴, R⁵ and R⁶ is independently H, a C1 to C6 alkylgroup, or a C3-C20 aryl or heterocycle group. R¹ and R² and/or R¹ and R³and/or R⁴ and R⁵ and/or R⁵ and R⁶ may be joined to form cyclic chains.

Exemplary bis(formamidinato)disilanes include:

Exemplary bis(amidinato)disilanes include:

Exemplary organodisilane precursors wherein x=3, n=3, and each E=NRcontain both β-diketiminate and hydride functionalities and have thefollowing formula:

wherein R¹, R², R³, R⁴ and R⁵ is independently H, a C1 to C6 alkylgroup, or a C3-C20 aryl or heterocycle group. R¹ and R² and/or R² and R³and/or R³ and R⁴ and/or R⁴ and R⁵ may be joined to form cyclic chains.

Exemplary mono(β-diketiminate)disilanes include:

Exemplary organodisilane precursors wherein x=2, each n=3, and each E=NRcontain both β-diketiminate and hydride functionalities and have thefollowing formula:

wherein each R is independently H, a C1 to C6 alkyl group, or a C3-C20aryl or heterocycle group. Adjacent Rs may be joined to form cyclicchains.

Exemplary bis(β-diketiminate)disilanes include:

The (RN═(CR)_(n)—NR)SiH₂—SiH₃ or [(RN═(CR)_(n)—NR)H₂Si—]₂ precursors maybe synthesized by combining a hydrocarbon solution of SiXH₂SiH₃ or[—SiXH₂]₂, respectively, wherein X is Cl, Br, I, or triflate (SO₃CF₃),with a neat or hydrocarbon solution of one (for the mono disilane) ortwo (for the bis disilane) equivalents of the ligand compound, such asLi[RN—(CR)_(n)═NR], or two (for the mono disilane) or four (for the bisdisilane) equivalents of the protonated ligand H(RN—(CR)_(n)═NR) underan inert atmosphere, such as nitrogen, the outlet of the mixing flaskbeing connected to an oil bubbler to inhibit backflow of air andmoisture. Alternatively, the disclosed (RN═(CR)_(n)—NR)SiH₂—SiH₃ or[(RN═(CR)_(n)—NR)H₂Si—]₂ precursors may be synthesized by reaction ofCl₃Si—SiCl₃ with one (mono) or two (bis) equivalents of the ligandcompound Li[RN—(CR)_(n)═NR] or two (mono) or four (bis) equivalents ofthe ligand compound H[RN—(CR)_(n)═NR] followed by filtration andsubsequent reduction using a selected metal hydride, such as LAH(lithium aluminum hydride). In all synthesis routes, the resultingsolution may be stirred at room temperature overnight.

Exemplary hydrocarbon solutions suitable for these synthesis methodsinclude diethyl ether, pentane, hexane, or toluene. The resultingsuspension is filtered and the resulting solution distilled to removesolvent. Purification of the resulting liquid or solid is carried out bydistillation or sublimation, respectively. Except for the ligandcompounds Li[RN—(CR)_(n)═NR] all of the starting materials arecommercially available. The ligand compound may be synthesized bycombining a hydrocarbon solution of metalorganic salt (i.e., alkyllithium) to a hydrocarbon solution of the appropriate amidine (for n=1)or β-diketimine (for n=3).

Each E may be an oxygen atom. Due to the increased oxygen content whencompared to the N embodiments above, these molecules may be used toproduce silicon-containing films that also contain oxygen, such as SiO₂,SiOC, or SiON, or to tune the amount of oxygen in a SiO₂, SiOC, or SiONcontaining film. The oxygen content may also make these precursorssuitable for typical casting depositions conditions which may take placeunder a non-inert atmosphere.

One of ordinary skill in the art will recognize that embodiments inwhich n=1 may produce precursors having higher volatility and lowermelting points, being more suitable for vapor deposition. Embodiments inwhich n=3 may also be suitable for vapor deposition when the resultingsilicon-containing film also contains carbon. Embodiments in which n=3may also be suitable for casting deposition methods, such as spin-on ordip coating.

Exemplary organodisilane precursors wherein x=3, n=1, and each E=Ocontain both acetate and hydride functionalities and have the followingformula:

wherein R¹ is H, a C1 to C6 alkyl group, or a C3-C20 aryl or heterocyclegroup.

Exemplary mono(acetate)disilanes include:

Exemplary organodisilane precursors wherein x=2, each n=1, and each E=Ocontain both acetate and hydride functionalities and have the followingformula:

wherein R¹ and R² is independently H, a C1 to C6 alkyl group, or aC3-C20 aryl or heterocycle group.

Exemplary bis(acetate)disilanes include:

Exemplary organodisilane precursors wherein x=3, n=3, and each E is Ocontain both diketonate and hydride functionalities and have thefollowing formula:

wherein R¹, R² and R³ is independently H, a C1 to C6 alkyl group, or aC3-C20 aryl or heterocycle group. R¹ and R² and/or R² and R³ may bejoined to form cyclic chains.

Exemplary mono(β-diketonate)disilanes include:

Exemplary organodisilane precursors wherein x=2, n=3, and each E is Ocontain both diketonate and hydride functionalities and have thefollowing formula:

wherein each R is independently H, a C1 to C6 alkyl group, or a C3-C20aryl or heterocycle group. Adjacent Rs may be joined to form cyclicchains.

Exemplary bis(β-diketonate)disilanes include:

The (O—(CR)_(n)═O)SiH₂—SiH₃ or [(O—(CR)_(n)═O)H₂Si—]₂ precursors may besynthesized by combining a hydrocarbon solution of SiXH₂SiH₃ or[—SiXH₂]₂, respectively, wherein X is Cl, Br, I, or triflate (SO₃CF₃),with a neat or hydrocarbon solution of one (for the mono disilane) ortwo (for the bis disilane) equivalents of the ligand compound, such asLi[O—(CR)_(n)═O], or two (for the mono disilane) or four (for the bisdisilane) equivalents of the protonated ligand H(O—(CR)_(n)═O) under aninert atmosphere, such as nitrogen, the outlet of the mixing flask beingconnected to an oil bubbler to inhibit backflow of air and moisture.Alternatively, the disclosed (O—(CR)_(n)═O)SiH₂—SiH₃ or[(O—(CR)_(n)═O)H₂Si—]₂ precursors may be synthesized by reaction ofCl₃Si—SiCl₃ with one (for the mono disilane) or two (for the bisdisilane) equivalents of the ligand compound Li[O—(CR)_(n)═O] or two(for the mono disilane) or four (for the bis disilane) equivalents ofthe ligand compound H[O—(CR)_(n)═O] followed by filtration andsubsequent reduction using a selected metal hydride, such as LAH(lithium aluminum hydride). In all synthesis routes, the resultingsolution may be stirred at room temperature overnight.

Exemplary hydrocarbon solutions suitable for these synthesis methodsinclude diethyl ether, pentane, hexane, or toluene. The resultingsuspension is filtered and the resulting solution distilled to removesolvent. Purification of the resulting liquid or solid is carried out bydistillation or sublimation, respectively. Except for the ligandcompounds Li[O—(CR)_(n)═O] all of the starting materials arecommercially available. The ligand compound may be synthesized bycombining a hydrocarbon solution of metalorganic salt (i.e., alkyllithium) to a hydrocarbon solution of the appropriate acetate,carboxylic acid or carbon dioxide (for n=1) or β-diketone (for n=3).

Each E may be a sulfur atom. The presence of sulfur within the precursorstructure may improve the surface sticking coefficient thereby allowingfor a favorable increase in film deposition rates.

One of ordinary skill in the art will recognize that embodiments inwhich n=1 may produce precursors having higher volatility and lowermelting points, being more suitable for vapor deposition. Embodiments inwhich n=3 may also be suitable for vapor deposition when the resultingsilicon-containing film also contains carbon. Embodiments in which n=3may also be suitable for casting deposition methods, such as spin-on ordip coating.

Exemplary organodisilane precursors wherein x=3, n=1, and each E=Scontain both dithiocarboxylate and hydride functionalities and have thefollowing formula:

wherein R¹ is H, a C1 to C6 alkyl group, or a C3-C20 aryl or heterocyclegroup.

Exemplary mono(dithiocarboxylate)disilanes include:

Exemplary organodisilane precursors wherein x=2, each n=1, and each E=Scontain both dithiocarboxylate and hydride functionalities and have thefollowing formula:

wherein R¹ and R² is independently H, a C1 to C6 alkyl group, or aC3-C20 aryl or heterocycle group.

Exemplary bis(dithiocarboxylate)disilanes include:

Exemplary organodisilane precursors wherein x=3, n=3, and each E is Scontain both dithio-β-diketonate and hydride functionalities and havethe following formula:

wherein R¹, R² and R³ is independently H, a C1 to C6 alkyl group, or aC3-C20 aryl or heterocycle group. R¹ and R² and/or R² and R³ may bejoined to form cyclic chains.

Exemplary mono(dithio-3-diketonate)disilanes include:

Exemplary organodisilane precursors wherein x=2, n=3, and each E is Scontain both dithio-β-diketonate and hydride functionalities and havethe following formula:

wherein each R is independently H, a C1 to C6 alkyl group, or a C3-C20aryl or heterocycle group. Adjacent Rs may be joined to form cyclicchains.

Exemplary bis(dithio-β-diketonate)disilanes include:

The (S—(CR)_(n)═S)SiH₂—SiH₃ or [(S—(CR)_(n)═S)H₂Si—]₂ precursors may besynthesized by combining a hydrocarbon solution of SiXH₂SiH₃ or[—SiXH₂]₂, respectively, wherein X is Cl, Br, I, or triflate (SO₃CF₃),with a neat or hydrocarbon solution of one (for the mono disilane) ortwo (for the bis disilane) equivalents of the ligand compound, such asLi[S—(CR)_(n)═S], or two (for the monodisilane) or four (for the bisdisilane) equivalents of the protonated ligand H(S—(CR)_(n)═S) under aninert atmosphere, such as nitrogen, the outlet of the mixing flask beingconnected to an oil bubbler to inhibit backflow of air and moisture.Alternatively, the disclosed (S—(CR)_(n)═S)SiH₂—SiH₃ or[(S—(CR)_(n)═S)H₂Si—]₂ precursors may be synthesized by reaction ofCl₃Si—SiCl₃ with one (for the mono disilane) or two (for the bisdisilane) equivalents of the ligand compound Li[S—(CR)_(n)═S] or two(for the mono disilane) or four (for the bis disilane) equivalents ofthe ligand compound H[S—(CR)_(n)═S] followed by filtration andsubsequent reduction using a selected metal hydride such as LAH (lithiumaluminum hydride). In all synthesis routes, the resulting solution maybe stirred at room temperature overnight.

Exemplary hydrocarbon solutions suitable for these synthesis methodsinclude diethyl ether, pentane, hexane, or toluene. The resultingsuspension is filtered and the resulting solution distilled to removesolvent. Purification of the resulting liquid or solid is carried out bydistillation or sublimation, respectively. Except for the ligandcompounds Li[S—(CR)_(n)═S] all of the starting materials arecommercially available. The ligand compound may be synthesized bycombining a hydrocarbon solution of metalorganic salt (i.e., alkyllithium) to a hydrocarbon solution of the appropriate dithiocarboxylate,dithiocarboxylic acid, or carbon disulfide (for n=1) or β-dithioketone(for n=3). The dithio-β-diketone (for n=3) may be synthesized bythiolation of the corresponding β-diketone using H₂S/I₂ (see Benvenutiet al, Applied Catalysis A, 199, 2000, 123-132). followed by combining ahydrocarbon solution of metalorganic salt (i.e., alkyl lithium) to ahydrocarbon solution of the resultant.

E may be both NR and oxygen atoms. Due to their increased nitrogencontent when compared to the when every E is an oxygen atom, thesemolecules may be used to produce silicon-containing films that alsocontain nitrogen, such as SiN, SiCN, SiON, MSiN, or MSiON, wherein M isan element such as Hf, Zr, Ti, Nb, Ta, or Ge, or to tune the amount ofnitrogen in those films.

One of ordinary skill in the art will recognize that embodiments inwhich n=1 may produce precursors having higher volatility and lowermelting points, being more suitable for vapor deposition. Embodiments inwhich n=3 may also be suitable for vapor deposition when the resultingsilicon-containing film also contains carbon. Embodiments in which n=3may also be suitable for casting deposition methods, such as spin-on ordip coating.

Exemplary organodisilane precursors wherein x=3, n=1, one E is NR, andthe other E is O contain both amidate and hydride functionalities andhave the following formula:

wherein R¹ and R² is independently H, a C1 to C6 alkyl group, or aC3-C20 aryl or heterocycle group. R¹ and R² may be joined to form cyclicchains.

Exemplary mono(amidate)disilanes include:

Exemplary organodisilane precursors wherein x=2, each n=1, one E is NRand one E is O on each (E-(CR)_(n)-E) ligand contain both ketoiminateand hydride functionalities and have the following formula:

wherein R¹, R², R³, and R⁴ is independently H, a C1 to C6 alkyl group,or a C3-C20 aryl or heterocycle group. R¹ and R² and/or R³ and R⁴ may bejoined to form cyclic chains.

Exemplary bis(amidate)disilanes include:

Exemplary organodisilane precursors wherein x=3, n=3, one E is NR andone E is O contain both β-ketiminate and hydride functionalities andhave the following formula:

wherein R¹, R², R³ and R⁴ is independently H, a C1 to C6 alkyl group, ora C3-C20 aryl or heterocycle group. R¹ and R² and/or R² and R³ and/or R³and R⁴ may be joined to form cyclic chains.

Exemplary mono(β-ketiminate)disilanes include:

Exemplary organodisilane precursors wherein x=2, n=3, one E is NR andone E is O contain both β-ketiminate and hydride functionalities andhave the following formula:

wherein R¹, R², R³ and R⁴ is independently H, a C1 to C6 alkyl group, ora C3-C20 aryl or heterocycle group. R¹ and R² and/or R² and R³ and/or R³and R⁴ may be joined to form cyclic chains.

Exemplary bis(β-ketiminate)disilanes include:

The (RN—(CR)_(n)═O)SiH₂—SiH₃ or [(RN—(CR)_(n)═O)H₂Si—]₂ precursors maybe synthesized by combining a hydrocarbon solution of SiXH₂SiH₃ or[—SiXH₂]₂, respectively, wherein X is Cl, Br, I, or triflate (SO₃CF₃),with a neat or hydrocarbon solution of one (for the mono disilane) ortwo (for the bis disilane) equivalents of the ligand compound, such asLi[RN—(CR)_(n)═O], or two (for the mono disilane) or four (for the bisdisilane) equivalents of the protonated ligand H(RN—(CR)_(n)═O) under aninert atmosphere, such as nitrogen, the outlet of the mixing flask beingconnected to an oil bubbler to inhibit backflow of air and moisture.Alternatively, the disclosed (RN—(CR)_(n)═O)SiH₂—SiH₃ or[(RN—(CR)_(n)═O)H₂Si—]₂ precursors may be synthesized by reaction ofCl₃Si—SiCl₃ with one (for the mono disilane) or two (for the bisdisilane) equivalents of the ligand compound Li[RN—(CR)_(n)═O] or two(for the mono disilane) or four (for the bis disilane) equivalents ofthe ligand compound H[RN—(CR)_(n)═O] followed by filtration andsubsequent reduction using a selected metal hydride, such as LAH(lithium aluminum hydride). In all synthesis routes, the resultingsolution may be stirred at room temperature overnight.

Exemplary hydrocarbon solutions suitable for these synthesis methodsinclude diethyl ether, pentane, hexane, or toluene. The resultingsuspension is filtered and the resulting solution distilled to removesolvent. Purification of the resulting liquid or solid is carried out bydistillation or sublimation, respectively. Except for the ligandcompounds Li[RN—(CR)_(n)═O] all of the starting materials arecommercially available. The ligand compound may be synthesized bycombining a hydrocarbon solution of metalorganic salt (i.e., alkyllithium) to a hydrocarbon solution of the appropriate amidate (for n=1)or β-ketimine (for n=3).

E may be both NR and sulfur atoms. The presence of sulfur within theprecursor structure may improve the substrate sticking coefficientthereby allowing for a favorable increase in film deposition rates. Dueto their increased nitrogen content when compared to the when every E isan oxygen atom, these molecules may be used to producesilicon-containing films that also contain nitrogen, such as SiN, SiCN,SiON, MSiN, or MSiON, wherein M is an element such as Hf, Zr, Ti, Nb,Ta, or Ge, or to tune the amount of nitrogen in those films.

One of ordinary skill in the art will recognize that embodiments inwhich n=1 may produce precursors having higher volatility and lowermelting points, being more suitable for vapor deposition. Embodiments inwhich n=3 may also be suitable for vapor deposition when the resultingsilicon-containing film also contains carbon. Embodiments in which n=3may also be suitable for casting deposition methods, such as spin-on ordip coating.

Exemplary organodisilane precursors wherein x=3, n=1, one E is NR, andone E is S contain both thioamidate and hydride functionalities and havethe following formula:

wherein R¹ and R² is independently H, a C1 to C6 alkyl group, or aC3-C20 aryl or heterocycle group. R¹ and R² may be joined to form cyclicchains.

Exemplary mono(thioamidate)disilanes include:

Exemplary organodisilane precursors wherein x=2, n=1, one E is NR andone E is S on each (E-(CR)_(n)-E) ligand contain both thioamidate andhydride functionalities and have the following formula:

wherein R¹, R², R³, and R⁴ is independently H, a C1 to C6 alkyl group,or a C3-C20 aryl or heterocycle group. R¹ and R² and/or R³ and R⁴ may bejoined to form cyclic chains.

Exemplary bis(thioamidate)disilanes include:

Exemplary organodisilane precursors wherein x=3, n=3, one E is NR andone E is S contain both β-thioketiminate and hydride functionalities andhave the following formula:

wherein R¹, R², R³ and R⁴ is independently H, a C1 to C6 alkyl group, ora C3-C20 aryl or heterocycle group. R¹ and R² and/or R² and R³ and/or R³and R⁴ may be joined to form cyclic chains.

Exemplary mono(β-thioketiminate)disilanes include:

Exemplary organodisilane precursors wherein x=2, n=3, one E is NR andone E is S contain both β-thioketiminate and hydride functionalities andhave the following formula:

wherein each R is independently H, a C1 to C6 alkyl group, or a C3-C20aryl or heterocycle group. Adjacent Rs may be joined to form cyclicchains.

Exemplary bis(β-thioketiminate)disilanes include:

The (RN—(CR)_(n)═S)SiH₂—SiH₃ or [(RN—(CR)_(n)═S)H₂Si—]₂ precursors maybe synthesized by combining a hydrocarbon solution of SiXH₂SiH₃ or[—SiXH₂]₂, respectively, wherein X is Cl, Br, I, or triflate (SO₃CF₃),with a neat or hydrocarbon solution of one (for the mono disilane) ortwo (for the bis disilane) equivalents of the ligand compound, such asLi[RN—(CR)_(n)═S], or two (for the mono disilane) or four (for the bisdisilane) equivalents of the protonated ligand H(RN—(CR)_(n)═S) under aninert atmosphere, such as nitrogen, the outlet of the mixing flask beingconnected to an oil bubbler to inhibit backflow of air and moisture.Alternatively, the disclosed (RN—(CR)_(n)═S)SiH₂—SiH₃ or[(RN—(CR)_(n)═S)H₂Si—]₂ precursors may be synthesized by reaction ofCl₃Si—SiCl₃ with one (for the mono disilane) or two (for the bisdisilane) equivalents of the ligand compound Li[RN—(CR)_(n)═S] or two(for the mono disilane) or four (for the bis disilane) equivalents ofthe ligand compound H[RN—(CR)_(n)═S] followed by filtration andsubsequent reduction using a selected metal hydride such as LAH (lithiumaluminum hydride). In all synthesis routes, the resulting solution maybe stirred at room temperature overnight.

Exemplary hydrocarbon solutions suitable for these synthesis methodsinclude diethyl ether, pentane, hexane, or toluene. The resultingsuspension is filtered and the resulting solution distilled to removesolvent. Purification of the resulting liquid or solid is carried out bydistillation or sublimation, respectively. Except for the ligandcompounds Li[RN—(CR)_(n)═S] all of the starting materials arecommercially available. The ligand compound for n=1 may be synthesizedby combining a hydrocarbon solution of metalorganic salt (i.e., alkyllithium) to a hydrocarbon solution of the appropriate thioamide. Theligand compound for n=3 may be synthesized by thiolation of thecorresponding β-ketimine using H₂S/I₂ (see Benvenuti et al, AppliedCatalysis A, 199, 2000, 123-132) followed by combining a hydrocarbonsolution of metalorganic salt (i.e., alkyl lithium) to a hydrocarbonsolution of the resultant β-thioketimine.

E may be both oxygen and sulfur atoms. The presence of sulfur within theprecursor structure may improve the substrate sticking coefficientthereby allowing for a favorable increase in film deposition rates. Theoxygen content may result in silicon-containing films that also containoxygen, such as SiO₂, SiOC, or SiON, or to tune the amount of oxygen ina SiO₂, SiOC, or SiON containing film.

One of ordinary skill in the art will recognize that embodiments inwhich n=1 may produce precursors having higher volatility and lowermelting points, being more suitable for vapor deposition. Embodiments inwhich n=3 may also be suitable for vapor deposition when the resultingsilicon-containing film also contains carbon. Embodiments in which n=3may also be suitable for casting deposition methods, such as spin-on ordip coating.

Exemplary organodisilane precursors wherein x=3, n=1, one E is O, andone E is S contain both thiocarboxylate and hydride functionalities andhave the following formula:

wherein R¹ is H, a C1 to C6 alkyl group, or a C3-C20 aryl or heterocyclegroup.

Exemplary mono(thiocarboxylate)disilanes include:

Exemplary organodisilane precursors wherein x=2, each n=1, one E is O,and one E is S on each (E-(CR)_(n)-E) ligand contain boththiocarboxylate and hydride functionalities and have the followingformula:

wherein R¹ and R² is independently H, a C1 to C6 alkyl group, or aC3-C20 aryl or heterocycle group.

Exemplary bis(thiocarboxylate)disilanes include:

Exemplary organodisilane precursors wherein x=3, n=3, one E is O and oneE is S contain both β-thioketonate and hydride functionalities and havethe following formula:

wherein R¹, R² and R³ is independently H, a C1 to C6 alkyl group, or aC3-C20 aryl or heterocycle group. R¹ and R² and/or R² and R³ may bejoined to form cyclic chains.

Exemplary mono(β-thioketonate)disilanes include:

Exemplary organodisilane precursors wherein x=2, n=3, one E is O and oneE is S contain both β-thioketonate and hydride functionalities and havethe following formula:

wherein each R is independently H, a C1 to C6 alkyl group, or a C3-C20aryl or heterocycle group. Adjacent Rs may be joined to form cyclicchains.

Exemplary bis(β-thioketonate)disilanes include:

The (O—(CR)_(n)═S)SiH₂—SiH₃ or [(O—(CR)_(n)═S)H₂Si—]₂ precursors may besynthesized by combining a hydrocarbon solution of SiXH₂SiH₃ or[—SiXH₂]₂, respectively, wherein X is Cl, Br, I, or triflate (SO₃CF₃),with a neat or hydrocarbon solution of one (for the mono disilane) ortwo (for the bis disilane) equivalents of the ligand compound, such asLi[O—(CR)_(n)═S], or two (for the mono disilane) or four (for the bisdisilane) equivalents of the protonated ligand H(O—(CR)_(n)═S) under aninert atmosphere, such as nitrogen, the outlet of the mixing flask beingconnected to an oil bubbler to inhibit backflow of air and moisture.Alternatively, the disclosed (O—(CR)_(n)═S)SiH₂—SiH₃ or[(O—(CR)_(n)═S)H₂Si—]₂ precursors may be synthesized by reaction ofCl₃Si—SiCl₃ with one (for the mono disilane) or two (for the bisdisilane) equivalents of the ligand compound Li[O—(CR)_(n)═S] or two(for the mono disilane) or four (for the bis disilane) equivalents ofthe ligand compound H[O—(CR)_(n)═S] followed by filtration andsubsequent reduction using a selected metal hydride, such as LAH(lithium aluminum hydride). In all synthesis routes, the resultingsolution may be stirred at room temperature overnight.

Exemplary hydrocarbon solutions suitable for these synthesis methodsinclude diethyl ether, pentane, hexane, or toluene. The resultingsuspension is filtered and the resulting solution distilled to removesolvent. Purification of the resulting liquid or solid is carried out bydistillation or sublimation, respectively. Except for the ligandcompounds Li[O—(CR)_(n)═S] all of the starting materials arecommercially available. The ligand compound for n=1 may be synthesizedby combining a hydrocarbon solution of metalorganic salt (i.e., alkyllithium) to a hydrocarbon solution of the appropriate thiocarboxylate,thiocarboxylic acid, or carbonyl sulfide. The ligand compound for n=3may be synthesized by thiolation of the corresponding β-diketone usingH₂S/I₂ (see Benvenuti et al, Applied Catalysis A, 199, 2000, 123-132)followed by combining a hydrocarbon solution of metalorganic salt (i.e.,alkyl lithium) to a hydrocarbon solution of the resultantβ-thioketimine.

To ensure process reliability, the resulting Si-containing film formingcomposition may be purified by continuous or fractional batchdistillation or sublimation prior to comprise between approximately 90%w/w to approximately 100% w/w of the organodisilane precursor, andpreferably between approximately 99% w/w to approximately 100% w/w. TheSi-containing film forming compositions may contain any of the followingimpurities: undesired congeneric species; solvents; chlorinated metalcompounds; or other reaction products. Preferably, the total quantity ofthese impurities is below approximately 0.1% w/w.

The concentration of each of hexane, substituted hexane, pentane,substituted pentane, dimethoxy ether, or anisole in the purifiedmaterial may range from approximately 0% w/w to approximately 5% w/w,preferably from approximately 0% w/w to approximately 0.1% w/w. Solventsmay be used in the composition's synthesis. Separation of the solventsfrom the composition may be difficult if both have similar boilingpoints. Cooling the mixture may produce solid precursor in liquidsolvent, which may be separated by filtration. Vacuum distillation mayalso be used, provided the precursor product is not heated aboveapproximately its decomposition point.

In one embodiment the disclosed Si-containing film forming compositioncontains between approximately 0% v/v and approximately 5% v/v,preferably less than approximately 1% v/v, more preferably less thanapproximately 0.1% v/v, and even more preferably less than approximately0.01% v/v of any of its undesired congeneric species, reactants, orother reaction products. This embodiment may provide better processrepeatability. This embodiment may be produced by distillation orsublimation of the Si-containing film forming composition. In analternate embodiment, the disclosed Si-containing film formingcompositions may contain between approximately 5% v/v and approximately50% v/v of the organodisilane precursor, particularly when the mixtureprovides improved process parameters or isolation of the targetprecursor is too difficult or expensive. For example, a mixture oforganodisilane precursors may produce a stable, liquid mixture suitablefor spin-on or vapor deposition.

The concentration of trace metals and metalloids in the Si-containingfilm forming composition may each range from approximately 0 ppb toapproximately 100 ppb, and more preferably from approximately 0 ppb toapproximately 10 ppb. The concentration of X (wherein X═Cl, Br, I, or F)in the purified Si-containing film forming composition may range fromapproximately 0 ppm to approximately 100 ppm and more preferably fromapproximately 0 ppm to approximately 10 ppm.

The Si-containing film forming compositions may be delivered to asemiconductor processing tool by the disclosed Si-containing filmforming composition delivery devices. FIGS. 1 and 2 show two embodimentsof the disclosed delivery devices 1.

FIG. 1 is a side view of one embodiment of the Si-containing filmforming composition delivery device 1. In FIG. 1, the disclosedSi-containing film forming compositions 10 are contained within acontainer 20 having two conduits, an inlet conduit 30 and an outletconduit 40. One of ordinary skill in the precursor art will recognizethat the container 20, inlet conduit 30, and outlet conduit 40 aremanufactured to prevent the escape of the gaseous form of theSi-containing film forming composition 10, even at elevated temperatureand pressure.

For pyrophoric compositions, such as SiH₃—SiH₂—^(iPr)N-amd, the deliverydevice must be leak tight and be equipped with valves that do not permiteven minute amounts of the material. Suitable valves includespring-loaded or tied diaphragm valves. The valve may further comprise arestrictive flow orifice (RFO). The delivery device should be connectedto a gas manifold and in an enclosure. The gas manifold should permitthe safe evacuation and purging of the piping that may be exposed to Airwhen the delivery device is replaced so that any residual amounts of thepyrophoric material does not react. The enclosure should be equippedwith sensors and fire control capability to control the fire in the caseof a pyrophoric material release. The gas manifold should also beequipped with isolation valves, vacuum generators, and permit theintroduction of a purge gas at a minimum.

The delivery device fluidly connects to other components of thesemiconductor processing tool, such as the gas cabinet disclosed above,via valves 35 and 45. Preferably, the delivery device 20, inlet conduit30, valve 35, outlet conduit 40, and valve 45 are made of 316L EP or 304stainless steel.

However, one of ordinary skill in the art will recognize that othernon-reactive materials may also be used in the teachings herein and thatany corrosive Si-containing film forming compositions 10 may require theuse of more corrosion-resistant materials, such as Hastelloy or Inconel.

In FIG. 1, the end 31 of inlet conduit 30 is located above the surface11 of the Si-containing film forming composition 10, whereas the end 41of the outlet conduit 40 is located below the surface 11 of theSi-containing film forming composition 10. In this embodiment, theSi-containing film forming composition 10 is preferably in liquid form.An inert gas, including but not limited to nitrogen, argon, helium, andmixtures thereof, may be introduced into the inlet conduit 30. The inertgas pressurizes the delivery device 20 so that the liquid Si-containingfilm forming composition 10 is forced through the outlet conduit 40 andto components in the semiconductor processing tool (not shown). Thesemiconductor processing tool may include a vaporizer which transformsthe liquid Si-containing film forming composition 10 into a vapor, withor without the use of a carrier gas such as helium, argon, nitrogen ormixtures thereof, in order to deliver the vapor to a chamber where awafer to be repaired is located and treatment occurs in the vapor phase.Alternatively, the liquid Si-containing film forming composition 10 maybe delivered directly to the wafer surface as a jet or aerosol.

FIG. 2 is a side view of a second embodiment of the Si-containing filmforming composition delivery device 1. In FIG. 2, the end 31 of inletconduit 30 is located below the surface 11 of the Si-containing filmforming composition 10, whereas the end 41 of the outlet conduit 40 islocated above the surface 11 of the Si-containing film formingcomposition 10. FIG. 2, also includes an optional heating element 25,which may increase the temperature of the Si-containing film formingcomposition 10. In this embodiment, the Si-containing film formingcomposition 10 may be in solid or liquid form. An inert gas, includingbut not limited to nitrogen, argon, helium, and mixtures thereof, isintroduced into the inlet conduit 30. The inert gas bubbles through theSi-containing film forming composition 10 and carries a mixture of theinert gas and vaporized Si-containing film forming composition 10 to theoutlet conduit 40 and on to the components in the semiconductorprocessing tool.

Both FIGS. 1 and 2 include valves 35 and 45. One of ordinary skill inthe art will recognize that valves 35 and 45 may be placed in an open orclosed position to allow flow through conduits 30 and 40, respectively.Either delivery device 1 in FIG. 1 or 2, or a simpler delivery devicehaving a single conduit terminating above the surface of any solid orliquid present, may be used if the Si-containing film formingcomposition 10 is in vapor form or if sufficient vapor pressure ispresent above the solid/liquid phase. In this case, the Si-containingfilm forming composition 10 is delivered in vapor form through theconduit 30 or 40 simply by opening the valve 35 in FIG. 1 or 45 in FIG.2, respectively. The delivery device 1 may be maintained at a suitabletemperature to provide sufficient vapor pressure for the Si-containingfilm forming composition 10 to be delivered in vapor form, for exampleby the use of an optional heating element 25.

While FIGS. 1 and 2 disclose two embodiments of the Si-containing filmforming composition delivery device 1, one of ordinary skill in the artwill recognize that the inlet conduit 30 and outlet conduit 40 may bothbe located above or below the surface 11 of the Si-containing filmforming composition 10 without departing from the disclosure herein.Furthermore, inlet conduit 30 may be a filling port. Finally, one ofordinary skill in the art will recognize that the disclosedSi-containing film forming composition may be delivered to semiconductorprocessing tools using other delivery devices, such as the ampoulesdisclosed in WO 2006/059187 to Jurcik et al., without departing from theteachings herein.

Also disclosed are methods of using the disclosed Si-containing filmforming compositions for vapor deposition methods. The disclosed methodsprovide for the use of the Si-containing film forming composition fordeposition of silicon-containing films. The disclosed methods may beuseful in the manufacture of semiconductor, photovoltaic, LCD-TFT, orflat panel type devices. The method includes: providing a substrate;providing a vapor including at least one of the disclosed Si-containingfilm forming compositions: and contacting the vapor with the substrate(and typically directing the vapor to the substrate) to form asilicon-containing layer on at least one surface of the substrate.

The disclosed methods also provide for forming a bimetal-containinglayer on a substrate using a vapor deposition process and, moreparticularly, for deposition of SiMO_(x) films wherein x is 4 and M isTa, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, lanthanides(such as Er), or combinations thereof. The disclosed methods may beuseful in the manufacture of semiconductor, photovoltaic, LCD-TFT, orflat panel type devices. The method includes: providing a substrate;providing a vapor including at least one of the disclosed Si-containingfilm forming compositions and contacting the vapor with the substrate(and typically directing the vapor to the substrate) to form a bimetal-containing layer on at least one surface of the substrate. Anoxygen source, such as O₃, O₂, H₂O, NO, H₂O₂, acetic acid, formalin,para-formaldehyde, oxygen radicals thereof, and combinations thereof,but preferably O₃ or plasma treated O₂ may also be provided with thevapor.

The disclosed Si-containing film forming compositions may depositSi-containing films using any vapor deposition methods known in the art.Examples of suitable vapor deposition methods include chemical vapordeposition (CVD) or atomic layer deposition (ALD). Exemplary CVD methodsinclude thermal CVD, plasma enhanced CVD (PECVD), pulsed CVD (PCVD), lowpressure CVD (LPCVD), sub-atmospheric CVD (SACVD) or atmosphericpressure CVD (APCVD), flowable CVD (f-CVD), hot-wire CVD (HWCVD, alsoknown as cat-CVD, in which a hot wire serves as an energy source for thedeposition process), radicals incorporated CVD, and combinationsthereof. Exemplary ALD methods include thermal ALD, plasma enhanced ALD(PEALD), spatial isolation ALD, hot-wire ALD (HWALD), radicalsincorporated ALD, and combinations thereof. Super critical fluiddeposition may also be used. The deposition method is preferably ALD,spatial ALD, or PE-ALD in order to provide suitable step coverage andfilm thickness control.

The vapor of the Si-containing film forming composition is introducedinto a reaction chamber containing at least one substrate. Thetemperature and the pressure within the reaction chamber and thetemperature of the substrate are held at conditions suitable for vapordeposition of at least part of the organodisilane precursor onto thesubstrate. In other words, after introduction of the vaporizedcomposition into the chamber, conditions within the chamber are suchthat at least part of the precursor is deposited onto the substrate toform the silicon-containing film. A reactant may also be used to help information of the Si-containing layer.

The reaction chamber may be any enclosure or chamber of a device inwhich deposition methods take place, such as, without limitation, aparallel-plate type reactor, a cold-wall type reactor, a hot-wall typereactor, a single-wafer reactor, a multi-wafer reactor, or other suchtypes of deposition systems. All of these exemplary reaction chambersare capable of serving as an ALD reaction chamber. The reaction chambermay be maintained at a pressure ranging from about 0.5 mTorr to about 20Torr. In addition, the temperature within the reaction chamber may rangefrom about 20° C. to about 600° C. One of ordinary skill in the art willrecognize that the temperature may be optimized through mereexperimentation to achieve the desired result.

The temperature of the reactor may be controlled by either controllingthe temperature of the substrate holder or controlling the temperatureof the reactor wall. Devices used to heat the substrate are known in theart. The reactor wall is heated to a sufficient temperature to obtainthe desired film at a sufficient growth rate and with desired physicalstate and composition. A non-limiting exemplary temperature range towhich the reactor wall may be heated includes from approximately 20° C.to approximately 600° C. When a plasma deposition process is utilized,the deposition temperature may range from approximately 20° C. toapproximately 550° C. Alternatively, when a thermal process isperformed, the deposition temperature may range from approximately 300°C. to approximately 600° C.

Alternatively, the substrate may be heated to a sufficient temperatureto obtain the desired silicon-containing film at a sufficient growthrate and with desired physical state and composition. A non-limitingexemplary temperature range to which the substrate may be heatedincludes from 150° C. to 600° C. Preferably, the temperature of thesubstrate remains less than or equal to 500° C.

The type of substrate upon which the silicon-containing film will bedeposited will vary depending on the final use intended. In someembodiments, the substrate may be a patterned photoresist film made ofhydrogenated carbon, for example CH_(x), wherein x is greater than zero.In some embodiments, the substrate may be chosen from oxides which areused as dielectric materials in MIM, DRAM, or FeRam technologies (forexample, ZrO₂ based materials, HfO₂ based materials, TiO₂ basedmaterials, rare earth oxide based materials, ternary oxide basedmaterials, etc.) or from nitride-based films (for example, TaN) that areused as an oxygen barrier between copper and the low-k layer. Othersubstrates may be used in the manufacture of semiconductors,photovoltaics, LCD-TFT, or flat panel devices. Examples of suchsubstrates include, but are not limited to, solid substrates such asmetal nitride containing substrates (for example, TaN, TiN, WN, TaCN,TiCN, TaSiN, and TiSiN); insulators (for example, SiO₂, Si₃N₄, SiON,HfO₂, Ta₂O₅, ZrO₂, TiO₂, Al₂O₃, and barium strontium titanate); or othersubstrates that include any number of combinations of these materials.The actual substrate utilized may also depend upon the specificprecursor embodiment utilized. In many instances though, the preferredsubstrate utilized will be selected from hydrogenated carbon, TiN, SRO,Ru, and Si type substrates, such as polysilicon or crystalline siliconsubstrates.

The substrate may be patterned to include vias or trenches having highaspect ratios. For example, a conformal Si-containing film, such asSiO₂, may be deposited using any ALD technique on a through silicon via(TSV) having an aspect ratio ranging from approximately 20:1 toapproximately 100:1.

The Si-containing film forming compositions may be supplied either inneat form or in a blend with a solvent suitable for vapor deposition,such as toluene, ethyl benzene, xylene, mesitylene, decane, dodecane,octane, hexane, pentane, tertiary amines, acetone, tetrahydrofuran,ethanol, ethylmethylketone, 1,4-dioxane, or others. Alternatively, theSi-containing film forming composition may comprise a solvent suitablefor casting deposition, such as naphtha, methylisobutylketone (MIBK),n-methylisobutylketone (NMIBK), or combinations thereof. One of ordinaryskill in the art will recognize that the casting deposition solution mayfurther comprise pH regulators or surfactants. The disclosed precursorsmay be present in varying concentrations in the solvent. For example,the resulting concentration of the vapor deposition solution may rangefrom approximately 0.01 M to approximately 2 M. One of ordinary skill inthe art will recognize that the molarity of the casting depositionsolution is directly proportional to the desired film thickness and mayadjust the molarity accordingly.

For vapor deposition, the neat or blended organodisilane precursors areintroduced into a reactor in vapor form by conventional means, such astubing and/or flow meters. The precursor in vapor form may be producedby vaporizing the neat or blended precursor solution through aconventional vaporization step such as direct vaporization,distillation, by bubbling, or by using a sublimator such as the onedisclosed in PCT Publication WO2009/087609 to Xu et al. The neat orblended precursor may be fed in liquid state to a vaporizer where it isvaporized before it is introduced into the reactor. Alternatively, theneat or blended precursor may be vaporized by passing a carrier gas intoa container containing the precursor or by bubbling of the carrier gasinto the precursor. The carrier gas may include, but is not limited to,Ar, He, or N₂, and mixtures thereof. Bubbling with a carrier gas mayalso remove any dissolved oxygen present in the neat or blendedprecursor solution. The carrier gas and precursor are then introducedinto the reactor as a vapor.

If necessary, the container may be heated to a temperature that permitsthe Si-containing film forming composition to be in its liquid phase andto have a sufficient vapor pressure. The container may be maintained attemperatures in the range of, for example, 0-150° C. Those skilled inthe art recognize that the temperature of the container may be adjustedin a known manner to control the amount of Si-containing film formingcomposition vaporized.

In addition to the disclosed precursor, a reaction gas may also beintroduced into the reactor. The reaction gas may be an oxidizing agentsuch as one of O₂; O₃; H₂O; H₂O₂; oxygen containing radicals such as O.or OH.; NO; NO₂; carboxylic acids such as formic acid, acetic acid,propionic acid; radical species of NO, NO₂, or the carboxylic acids;para-formaldehyde; and mixtures thereof. Preferably, the oxidizing agentis selected from the group consisting of O₂, O₃, H₂O, H₂O₂, oxygencontaining radicals thereof such as O. or OH., and mixtures thereof.Preferably, when an ALD process is performed, the reactant is plasmatreated oxygen, ozone, or combinations thereof. When an oxidizing gas isused, the resulting silicon containing film will also contain oxygen.

Alternatively, the reaction gas may be a reducing agent such as one ofH₂, NH₃, (SiH₃)₃N, hydridosilanes (such as SiH₄, Si₂H₆, Si₃H₈, Si₄H₁₀,Si₅H₁₀, Si₆H₁₂), chlorosilanes and chloropolysilanes (such as SiHCl₃,SiH₂Cl₂, SIH₃Cl, Si₂Cl₆, Si₂HCl₅, Si₃Cl₈), alkylsilanes (such as(CH₃)₂SiH₂, (C₂H₅)₂SiH₂, (CH₃)SiH₃, (C₂H₅)SiH₃), hydrazines (such asN₂H₄, MeHNNH₂, MeHNNHMe), organic amines (such as N(CH₃)H₂, N(C₂H₅)H₂,N(CH₃)₂H, N(C₂H₅)₂H, N(CH₃)₃, N(C₂H₅)₃, (SiMe₃)₂NH), pyrazoline,pyridine, B-containing molecules (such as B₂H₆,9-borabicyclo[3,3,1]none, trimethylboron, triethylboron, borazine),alkyl metals (such as trimethylaluminum, triethylaluminum, dimethylzinc,diethylzinc), radical species thereof, and mixtures thereof. Preferably,the reducing agent is H₂, NH₃, SiH₄, Si₂H₆, Si₃H₈, SiH₂Me₂, SiH₂Et₂,N(SiH₃)₃, hydrogen radicals thereof, or mixtures thereof. When areducing agent is used, the resulting silicon containing film may bepure Si.

The reaction gas may be treated by plasma, in order to decompose thereaction gas into its radical form. N₂ may also be utilized as areducing agent when treated with plasma. For instance, the plasma may begenerated with a power ranging from about 50 W to about 500 W,preferably from about 100 W to about 200 W. The plasma may be generatedor present within the reactor itself. Alternatively, the plasma maygenerally be at a location removed from the reactor, for instance, in aremotely located plasma system. One of skill in the art will recognizemethods and apparatus suitable for such plasma treatment.

The disclosed Si-containing film forming compositions may also be usedwith a halosilane or polyhalodisilane, such as hexachlorodisilanepentachlorodisilane, or tetrachlorodisilane, and one or more reactantgases to form SiN or SiCN films, as disclosed in PCT Publication NumberWO2011/123792, the entire contents of which are incorporated herein intheir entireties and the process of which is disclosed in more detailbelow.

When the desired silicon-containing film also contains another element,such as, for example and without limitation, Ta, Hf, Nb, Mg, Al, Sr, Y,Ba, Ca, As, Sb, Bi, Sn, Pb, Co, lanthanides (such as Er), orcombinations thereof, the reactants may include a metal-containingprecursor which is selected from, but not limited to, metal alkyls, suchas Ln(RCp)₃ or Co(RCp)₂, metal amines, such as Nb(Cp)(NtBu)(Nme₂)₃ andany combination thereof.

The Si-containing film forming composition and one or more reactants maybe introduced into the reaction chamber simultaneously (chemical vapordeposition), sequentially (atomic layer deposition), or in othercombinations. For example, the Si-containing film forming compositionmay be introduced in one pulse and two additional metal sources may beintroduced together in a separate pulse [modified atomic layerdeposition]. Alternatively, the reaction chamber may already contain thereactant prior to introduction of the Si-containing film formingcomposition. The reactant may be passed through a plasma systemlocalized or remotely from the reaction chamber, and decomposed toradicals. Alternatively, the Si-containing film forming composition maybe introduced to the reaction chamber continuously while other metalsources are introduced by pulse (pulsed-chemical vapor deposition). Ineach example, a pulse may be followed by a purge or evacuation step toremove excess amounts of the component introduced. In each example, thepulse may last for a time period ranging from about 0.01 s to about 10s, alternatively from about 0.3 s to about 3 s, alternatively from about0.5 s to about 2 s. In another alternative, the Si-containing filmforming composition and one or more reactants may be simultaneouslysprayed from a shower head under which a susceptor holding severalwafers is spun (spatial ALD).

In one non-limiting exemplary atomic layer deposition type process, thevapor phase of a Si-containing film forming composition is introducedinto the reaction chamber, where it is contacted with a suitablesubstrate. Excess composition may then be removed from the reactionchamber by purging and/or evacuating the reaction chamber. An oxygensource is introduced into the reaction chamber where it reacts with theabsorbed organodisilane precursor in a self-limiting manner. Any excessoxygen source is removed from the reaction chamber by purging and/orevacuating the reaction chamber. If the desired film is a silicon oxidefilm, this two-step process may provide the desired film thickness ormay be repeated until a film having the necessary thickness has beenobtained.

Alternatively, if the desired film is a silicon metal oxide film (i.e.,SiMO_(x), wherein x may be 4 and M is Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca,As, Sb, Bi, Sn, Pb, Co, lanthanides (such as Er), or combinationsthereof), the two-step process above may be followed by introduction ofa vapor of a second precursor into the reaction chamber. The secondprecursor will be selected based on the nature of the SiMO_(x) filmbeing deposited. After introduction into the reaction chamber, thesecond precursor is contacted with the substrate. Any excess secondprecursor is removed from the reaction chamber by purging and/orevacuating the reaction chamber. Once again, an oxygen source may beintroduced into the reaction chamber to react with the second precursor.Excess oxygen source is removed from the reaction chamber by purgingand/or evacuating the reaction chamber. If a desired film thickness hasbeen achieved, the process may be terminated. However, if a thicker filmis desired, the entire four-step process may be repeated. By alternatingthe provision of the Si-containing film forming composition, secondprecursor, and oxygen source, a film of desired composition andthickness can be deposited.

Additionally, by varying the number of pulses, films having a desiredstoichiometric M:Si ratio may be obtained. For example, a SiMO₂ film maybe obtained by having one pulse of the Si-containing film formingcomposition and one pulse of the second precursor, with each pulse beingfollowed by pulses of the oxygen source. However, one of ordinary skillin the art will recognize that the number of pulses required to obtainthe desired film may not be identical to the stoichiometric ratio of theresulting film.

In another alternative and as disclosed in WO WO2011/123792, dense SiCNfilms may be deposited using an ALD method with hexachlorodisilane(HCDS) or pentachlorodisilane (PCDS), the disclosed Si-containing filmforming composition, and an ammonia co-reactant. The reaction chambermay be controlled at 5 Torr, 550° C., with a 55 sccm continuous flow ofAr. An approximately 10 second long pulse of the Si-containing filmforming composition at a flow rate of approximately 1 sccm is introducedinto the reaction chamber. The composition is purged from the reactionchamber with an approximately 55 sccm flow of Ar for approximately 30seconds. An approximately 10 second pulse of HCDS at a flow rate ofapproximately 1 sccm is introduced into the reaction chamber. The HCDSis purged from the reaction chamber with an approximately 55 sccm flowof Ar for approximately 30 seconds. An approximately 10 second longpulse of NH₃ at a flow rate of approximately 50 sccm is introduced intothe reaction chamber. The NH₃ is purged from the reaction chamber withan approximately 55 sccm flow of Ar for approximately 10 seconds. These6 steps are repeated until the deposited layer achieves a suitablethickness. One of ordinary skill in the art will recognize that theintroductory pulses may be simultaneous when using a spatial ALD device.As described in PCT Pub No WO2011/123792, the order of the introductionof the precursors may be varied and the deposition may be performed withor without the NH₃ co-reactant in order to tune the amounts of carbonand nitrogen in the SiCN film.

In yet another alternative, a silicon-containing film may be depositedby the flowable PECVD method disclosed in U.S. Pat. App. Pub. No.2014/0051264 using the disclosed compositions and a radical nitrogen- oroxygen-containing co-reactant. The radical nitrogen- oroxygen-containing co-reactant, such as NH₃ or H₂O respectively, isgenerated in a remote plasma system. The radical co-reactant and thevapor phase of the disclosed compositions are introduced into thereaction chamber where they react and deposit the initially flowablefilm on the substrate. Applicants believe that the nitrogen atoms of thedisclosed N-containing organodisilane precursors and/or the sulfur atomsof the disclosed S-containing organodisilane precursors may help tofurther improve the flowability of the deposited film, resulting infilms containing fewer voids.

Also disclosed are methods of using the disclosed Si-containing filmforming compositions in casting deposition methods, such as spincoating, spray coating, dip coating or slit coating techniques. Thedisclosed methods provide for the use of the Si-containing film formingcomposition for deposition of silicon-containing films. The disclosedmethods may be useful in the manufacture of semiconductor, photovoltaic,LCD-TFT, or flat panel type devices. The method includes: applying theliquid form of the disclosed Si-containing film forming composition on asubstrate in a reactor: and forming the Si-containing layer on thesubstrate. As discussed previously, the liquid form of the disclosedSi-containing film forming composition may be a neat solution of theorganodisilane precursor or a mixture of the precursor with a solventand optional pH adjusters or surfactants. The liquid form of thedisclosed Si-containing film forming composition may be applied directlyto the center of the substrate or may be applied to the entire substrateby spraying. When applied directly to the center of the substrate, thesubstrate may be spun to utilize centrifugal forces to evenly distributethe composition over the substrate. Alternatively, the substrate may bedipped in the Si-containing film forming composition. The resulting filmmay be dried at an appropriate temperature for a period of time tovaporize any solvent or volatile components of the film. One of ordinaryskill in the art would recognize the appropriate temperature selectionbased on the solvent to be evaporated. During the vaporization process,a mist of water may be sprayed onto the substrate to promote thehydrolysis reaction of the film.

The disclosed organodisilane precursors in the Si-containing filmforming compositions may prove useful as monomers for the synthesis ofsilicon containing polymers. The Si-containing film forming compositionsmay be used to form spin-on dielectric film formulations, forpatternable films, or for anti-reflective films. For example, thedisclosed Si-containing film forming compositions may comprise a solventand applied to a substrate to form a film. If necessary, the substratemay be rotated to evenly distribute the Si-containing film formingcomposition across the substrate. One of ordinary skill in the art willrecognize that the viscosity of the Si-containing film formingcompositions will contribute as to whether rotation of the substrate isnecessary. The resulting film may be heated under an inert gas, such asArgon, Helium, or nitrogen and/or under reduced pressure. Alternatively,electron beams or ultraviolet radiation may be applied to the resultingfilm. The 8-9 hydrolysable groups of the disclosed organodisilaneprecursors (i.e., the direct Si—Si, Si—N, Si—O, Si—S, or Si—H bonds) mayprove useful to increase the connectivity of the polymer obtained.

The silicon-containing films resulting from the processes discussedabove may include Si, SiC, SiO₂, SiN, SiON, SiCN, SiCOH, pSiCOH, orMSiO_(x), wherein M is an element such as Hf, Zr, Ti, Nb, Ta, or Ge, andx may be 0-4, depending of course on the oxidation state of M. One ofordinary skill in the art will recognize that by judicial selection ofthe appropriate organodisilane precursor and co-reactants, the desiredfilm composition may be obtained.

Upon obtaining a desired film thickness, the film may be subject tofurther processing, such as thermal annealing, furnace-annealing, rapidthermal annealing, UV or e-beam curing, and/or plasma gas exposure.Those skilled in the art recognize the systems and methods utilized toperform these additional processing steps. For example, thesilicon-containing film may be exposed to a temperature ranging fromapproximately 200° C. and approximately 1000° C. for a time ranging fromapproximately 0.1 second to approximately 7200 seconds under an inertatmosphere, a H-containing atmosphere, a N-containing atmosphere, anO-containing atmosphere, or combinations thereof. Most preferably, thetemperature is 600° C. for less than 3600 seconds under a H-containingatmosphere. The resulting film may contain fewer impurities andtherefore may have improved performance characteristics. The annealingstep may be performed in the same reaction chamber in which thedeposition process is performed. Alternatively, the substrate may beremoved from the reaction chamber, with the annealing/flash annealingprocess being performed in a separate apparatus. Any of the abovepost-treatment methods, but especially thermal annealing, has been foundeffective to reduce carbon and nitrogen contamination of thesilicon-containing film.

It will be understood that many additional changes in the details,materials, steps, and arrangement of parts, which have been hereindescribed and illustrated in order to explain the nature of theinvention, may be made by those skilled in the art within the principleand scope of the invention as expressed in the appended claims. Thus,the present invention is not intended to be limited to the specificembodiments in the examples given above and/or the attached drawings.

We claim:
 1. A Si-containing film forming composition comprising anorganodisilane precursor having the formula:(E-(CR)_(n)-E)SiH₂—SiH_(x)-(E-(CR)_(n)-E)_(3-x) wherein x is 2 or 3;each n is independently 1 or 3; each (E-(CR)_(n)-E) group is amonoanionic bidentate ligand bonding to the Si through each E; each E isindependently chosen from NR, O or S; and each R is independentlyselected from the group consisting of H, a C1 to C6 alkyl group, and aC3-C20 aryl or heterocycle group.
 2. The Si-containing film formingcomposition of claim 1, wherein the organodisilane precursor has theformula:


3. The Si-containing film forming composition of claim 2, wherein theorganodisilane precursor has the formula:


4. The Si-containing film forming composition of claim 2, wherein theorganodisilane precursor has the formula:


5. The Si-containing film forming composition of claim 2, wherein theorganodisilane precursor has the formula:


6. The Si-containing film forming composition of claim 2, wherein theorganodisilane precursor has the formula:


7. The Si-containing film forming composition of claim 1, wherein theorganodisilane precursor has the formula:


8. The Si-containing film forming composition of claim 1, wherein theorganodisilane precursor has the formula:


9. The Si-containing film forming composition of claim 8, wherein theorganodisilane precursor has the formula:


10. The Si-containing film forming composition of claim 1, wherein theorganodisilane precursor has the formula:


11. A method of deposition a Si-containing layer on a substrate, themethod comprising: introducing a vapor of the organodisilane precursorof claim 1 into a reactor having a substrate disposed therein; anddepositing at least part of the organodisilane precursor onto thesubstrate to form a Si-containing layer using a vapor deposition method.12. The method of claim 11, further comprising introducing a co-reactantinto the reactor.
 13. The method of claim 11, wherein the vapordeposition process is a chemical vapor deposition process.
 14. Themethod of claim 11, wherein the vapor deposition process is an atomiclayer deposition (ALD) process.
 15. A method of forming a Si-containingfilm on a substrate, the method comprising forming a solution comprisingthe Si-containing film forming composition of claim 1; and contactingthe solution with the substrate via a spin coating, spray coating, dipcoating, or slit coating technique to form the Si-containing film. 16.The method of claim 11, wherein the organodisilane precursor has theformula:


17. The method of claim 11, wherein the organodisilane precursor has theformula:


18. The method of claim 11, wherein the organodisilane precursor has theformula:


19. The method of claim 15, wherein the organodisilane precursor has theformula:


20. The method of claim 15, wherein the organodisilane precursor has theformula: